Illustration of the Intrinsic Mechanism of Reconstructed Cu Clusters for Enhanced CO2 Electroreduction to Ethanol Production with Industrial Current Density.

Copper-based catalysts have been attracting increasing attention for CO2 electroreduction into value-added multicarbon chemicals. However, most Cu-based catalysts are designed for ethylene production, while ethanol production with high Faradaic efficiency at high current density still remains a great challenge. Herein, Cu clusters supported on single-atom Cu dispersed nitrogen-doped carbon (Cux/Cu-N/C) show ethanol Faradaic efficiency of ∼40% and partial current density of ∼350 mA cm-2. Quasi in situ X-ray photoelectron spectroscopy and operando X-ray absorption spectroscopy results suggest the generation of surface asymmetrical sites of Cu+ and Cu0 as well as Cu clusters by electrochemical reduction and reconstruction during the CO2 electroreduction process. Density functional theory calculations indicate that the interaction between Cu clusters and the Cu-N/C support enhances *CO adsorption, facilitates the C-C coupling step, and favors the hydrogenation rather than dehydroxylation of the critical intermediate *CHCOH toward ethanol in the bifurcation.

Exploring the Localization of Siderophore-Mediated Cargo Delivery in Gram-Negative Bacteria Using 3-Hydroxypyridin-4(1H)-one-Fluorescein Probes.

The design of siderophore-antibiotic conjugates is a promising strategy to overcome drug resistance in negative bacteria. However, accumulating studies have shown that only those antibiotics acting on the cell wall or cell membrane multiply their antibacterial effects when coupled with siderophores, while antibiotics acting on targets in the cytoplasm of bacteria do not show an obvious enhancement of their antibacterial effects when coupled with siderophores. To explore the causes of this phenomenon, we synthesized several conjugate probes using 3-hydroxypyridin-4(1H)-ones as siderophores and replacing the antibiotic cargo with 5-carboxyfluorescein (5-FAM) or malachite green (MG) cargo. By monitoring changes in the fluorescence intensity of FAM conjugate 20 in bacteria, the translocation of the conjugate across the outer membranes of Gram-negative pathogens was confirmed. Further, the use of the fluorogen activating protein(FAP)/MG system revealed that 3-hydroxypyridin-4(1H)-one-MG conjugate 26 was ultimately distributed mainly in the periplasm rather than being translocated into the cytosol of Escherichia coli and Pseudomonas aeruginosa PAO1. Additional mechanistic studies suggested that the uptake of the conjugate involved the siderophore-dependent iron transport pathway and the 3-hydroxypyridin-4(1H)-ones siderophore receptor-dependent mechanism. Meanwhile, we demonstrated that the conjugation of 3-hydroxypyridin-4(1H)-ones to the fluorescein 5-FAM can reduce the possibility of the conjugates crossing the membrane layers of mammalian Vero cells by passive diffusion, and the advantages of the mono-3-hydroxypyridin-4(1H)-ones as a delivery vehicle in the design of conjugates compared to the tri-3-hydroxypyridin-4(1H)-ones. Overall, this work reveals the localization rules of 3-hydroxypyridin-4(1H)-ones as siderophores to deliver the cargo into Gram-negative bacteria. It provides a theoretical basis for the subsequent design of siderophore-antibiotic conjugates, especially based on 3-hydroxypyridin-4(1H)-ones as siderophores.

Cajaninstilbene acid derivatives conjugated with siderophores of 3-hydroxypyridin-4(1H)-ones as novel antibacterial agents against Gram-negative bacteria based on the Trojan horse strategy.

The low permeability of the outer membrane of Gram-negative bacteria is a serious obstacle to the development of new antibiotics against them. Conjugation of antibiotic with siderophore based on the "Trojan horse strategy" is a promising strategy to overcome the outer membrane obstacle. In this study, series of antibacterial agents were designed and synthesized by conjugating the 3-hydroxypyridin-4(1H)-one based siderophores with cajaninstilbene acid (CSA) derivative 4 which shows good activity against Gram-positive bacteria by targeting their cell membranes but is ineffective against Gram-negative bacteria. Compared to the inactive parent compound 4, the conjugates 45c or 45d exhibits significant improvement in activity against Gram-negative bacteria, including Escherichia coli, Klebsiella pneumoniae and especially P. aeruginosa (minimum inhibitory concentrations, MICs = 7.8-31.25 µM). The antibacterial activity of the conjugates is attributed to the CSA derivative moiety, and the action mechanism is by disruption of bacterial cell membranes. Further studies on the uptake mechanisms showed that the bacterial siderophore-dependent iron transport system was involved in the uptake of the conjugates. In addition, the conjugates 45c and 45d showed a lower cytotoxic effects in vivo and in vitro and a positive therapeutic effect in the treatment of C. elegans infected by P. aeruginosa. Overall, our work describes a new class and a promising 3-hydroxypyridin-4(1H)-one-CSA derivative conjugates for further development as antibacterial agents against Gram-negative bacteria.

Surface Activation by Single Ru Atoms for Enhanced High-Temperature CO2 Electrolysis.

Cathodic CO2 adsorption and activation is essential for high-temperature CO2 electrolysis in solid oxide electrolysis cells (SOECs). However, the component of oxygen ionic conductor in the cathode displays limited electrocatalytic activity. Herein, stable single Ruthenium (Ru) atoms are anchored on the surface of oxygen ionic conductor (Ce0.8 Sm0.2 O2-δ , SDC) via the strong covalent metal-support interaction, which evidently modifies the electronic structure of SDC surface for favorable oxygen vacancy formation and enhanced CO2 adsorption and activation, finally evoking the electrocatalytic activity of SDC for high-temperature CO2 electrolysis. Experimentally, SOEC with the Ru1 /SDC-La0.6 Sr0.4 Co0.2 Fe0.8 O3-δ cathode exhibits a current density as high as 2.39 A cm-2 at 1.6 V and 800 °C. This work expands the application of single atom catalyst to the high-temperature electrocatalytic reaction in SOEC and provides an efficient strategy to tailor the electronic structure and electrocatalytic activity of SOEC cathode at the atomic scale.

Dimeric polybismuth heteroanion of [Rh@Bi10(RhCO)5]2- constructed using Bi10-bowl and square pyramidal Rh@(Rh-CO)5.

Redox reaction of the monovalent Rh2(CO)4Cl2 and Binn- (n = 2, 3) from K5Bi4 in ethylenediamine (en) solution produced the decabismuthide-hexarhodium dianion [Rh@Bi10(RhCO)5]2- (1a) wherein a novel Bi10-bowl was constructed from oxidized 2Bi3/2Bi2 open triangles/dimers, which was stabilized by strong bonding to a reduced Rh@(RhCO)5 square pyramid. Two 1a dianons are held together by weak interactions (van der Waals forces and spatial resistance) to form a dimer [Rh@Bi10(RhCO)5]24- (1). The structure and bonding of the novel polybismuthide heteroanion 1 are discussed.

Controlled synthesis of Mo2C micron flowers via vapor-liquid-solid method as enhanced electrocatalyst for hydrogen evolution reaction.

Mo2C demonstrates excellent performance in catalysis, and it has been found to possess excellent hydrogen evolution reaction (HER) catalytic activity and highly efficient nitrogen fixation. The catalytic activity of Mo2C is greatly influenced and restricted by the preparation method. Sintering and carbon deposition, which affect the catalytic activity of Mo2C, are inevitable in the traditional vapor-solid-solid (VSS) process. In this study, we report the controllable synthesis of α-Mo2C micron flowers by adjusting the growth temperature via a vapor-liquid-solid (VLS) process. The density of the Mo2C micron flowers is closely related to the concentration of Na2MoO4 aqueous solution. The as-grown Mo2C micron flowers dispersed with Pt are validated to be an enhanced collaborative electrocatalyst for HER against Pt/VSS-Mo2C.

How do housing prices affect innovation and entrepreneurship? Evidence from China.

This paper analyzes how housing prices affect innovation and entrepreneurship. We construct a city-level panel dataset including 281 cities between 2009 and 2019 by merging housing price data from China Statistical Yearbook for Regional Economy with innovation and entrepreneurship data from Peking University Open Research Data Platform. Our results suggest that housing prices are positively associated with the vitality of innovation and entrepreneurship (VIE). The results remain consistent with a series of robustness checks. We also find that rising house prices promote VIE through the wealth effect and the siphon effect. Spatial effect analysis further shows that housing prices not only positively affect the VIE of local cities, but also positively affect the VIE of neighboring cities. These findings imply the necessity of curbing the excessive rise of housing prices and decoupling public services and benefits related to homeownership.

3-Hydroxy-pyridin-4(1H)-ones as siderophores mediated delivery of isobavachalcone enhances antibacterial activity against pathogenic Pseudomonas aeruginosa.

The natural prenylated chalcone isobavachalcone (IBC) shows good antibacterial activity against Gram-positive bacteria but is ineffective against Gram-negative bacteria, most likely due to the outer membrane barrier of Gram-negative bacteria. The Trojan horse strategy has been shown to be an effective strategy to overcome the reduction in the permeability of the outer membrane of Gram-negative bacteria. In this study, eight different 3-hydroxy-pyridin-4(1H)-one-isobavachalcone conjugates were designed and synthesized based on the siderophore Trojan horse strategy. The conjugates exhibited 8- to 32-fold lower minimum inhibitory concentrations (MICs) and 32- to 177-fold lower half-inhibitory concentrations (IC50s) against Pseudomonas aeruginosa PAO1 as well as clinical multidrug-resistant (MDR) strains compared to the parent IBC under iron limitation. Further studies showed that the antibacterial activity of the conjugates was regulated by the bacterial iron uptake pathway under different iron concentration conditions. Studies on the antibacterial mechanism of conjugate 1b showed that it exerts antibacterial activity by disrupting cytoplasmic membrane integrity and inhibiting cell metabolism. Finally, conjugate 1b showed a lower cytotoxic effects on Vero cells than IBC and a positive therapeutic effect in the treatment of bacterial infections caused by Gram-negative bacteria PAO1. Overall, this work demonstrates that IBC can be delivered to Gram-negative bacteria when combined with 3-hydroxy-pyridin-4(1H)-ones as siderophores and provides a scientific basis for the development of effective antibacterial agents against Gram-negative bacteria.

Prominent Size Effects without a Depolarization Field Observed in Ultrathin Ferroelectric Oxide Membranes.

The increasing miniaturization of electronics requires a better understanding of material properties at the nanoscale. Many studies have shown that there is a ferroelectric size limit in oxides, below which the ferroelectricity will be strongly suppressed due to the depolarization field, and whether such a limit still exists in the absence of the depolarization field remains unclear. Here, by applying uniaxial strain, we obtain pure in-plane polarized ferroelectricity in ultrathin SrTiO_{3} membranes, providing a clean system with high tunability to explore ferroelectric size effects especially the thickness-dependent ferroelectric instability with no depolarization field. Surprisingly, the domain size, ferroelectric transition temperature, and critical strain for room-temperature ferroelectricity all exhibit significant thickness dependence. These results indicate that the stability of ferroelectricity is suppressed (enhanced) by increasing the surface or bulk ratio (strain), which can be explained by considering the thickness-dependent dipole-dipole interactions within the transverse Ising model. Our study provides new insights into ferroelectric size effects and sheds light on the applications of ferroelectric thin films in nanoelectronics.

Enhanced polarization and abnormal flexural deformation in bent freestanding perovskite oxides.

Recent realizations of ultrathin freestanding perovskite oxides offer a unique platform to probe novel properties in two-dimensional oxides. Here, we observe a giant flexoelectric response in freestanding BiFeO3 and SrTiO3 in their bent state arising from strain gradients up to 3.5 × 107 m-1, suggesting a promising approach for realizing ultra-large polarizations. Additionally, a substantial change in membrane thickness is discovered in bent freestanding BiFeO3, which implies an unusual bending-expansion/shrinkage effect in the ferroelectric membrane that has never been seen before in crystalline materials. Our theoretical model reveals that this unprecedented flexural deformation within the membrane is attributable to a flexoelectricity-piezoelectricity interplay. The finding unveils intriguing nanoscale electromechanical properties and provides guidance for their practical applications in flexible nanoelectromechanical systems.

Selective CO2 Electroreduction to Ethanol over a Carbon-Coated CuOx Catalyst.

The design of efficient copper(Cu)-based catalysts is critical for CO2 electroreduction into multiple carbon products. However, most Cu-based catalysts are favorable for ethylene production while selective production of ethanol with high Faradaic efficiency and current density still remains a great challenge. Herein, we design a carbon-coated CuOx (CuOx @C) catalyst through one-pot pyrolysis of Cu-based metal-organic framework (MOF), which exhibits high selectivity for CO2 electroreduction to ethanol with Faradaic efficiency of 46 %. Impressively, the partial current density of ethanol reaches 166 mA cm-2 , which is higher than that of most reported catalysts. Operando Raman spectra indicate that the carbon coating can efficiently stabilize Cu+ species under CO2 electroreduction conditions, which promotes the C-C coupling step. Density functional theory (DFT) calculations reveal that the carbon layer can tune the key intermediate *HOCCH goes the hydrogenation pathway toward ethanol production.

A Reconstructed Cu2 P2 O7 Catalyst for Selective CO2 Electroreduction to Multicarbon Products.

The electrochemical CO2 reduction reaction (CO2 RR) over Cu-based catalysts shows great potential for converting CO2 into multicarbon (C2+ ) fuels and chemicals. Herein, we introduce an A2 M2 O7 structure into a Cu-based catalyst through a solid-state reaction synthesis method. The Cu2 P2 O7 catalyst is electrochemically reduced to metallic Cu with a significant structure evolution from grain aggregates to highly porous structure under CO2 RR conditions. The reconstructed Cu2 P2 O7 catalyst achieves a Faradaic efficiency of 73.6 % for C2+ products at an applied current density of 350 mA cm-2 , remarkably higher than the CuO counterparts. The reconstructed Cu2 P2 O7 catalyst has a high electrochemically active surface area, abundant defects, and low-coordinated sites. In situ Raman spectroscopy and density functional theory calculations reveal that CO adsorption with bridge and atop configurations is largely improved on Cu with defects and low-coordinated sites, which decreased the energy barrier of the C-C coupling reaction for C2+ products.

Giant Thermal Transport Tuning at a Metal/Ferroelectric Interface.

Interfacial thermal transport plays a prominent role in the thermal management of nanoscale objects and is of fundamental importance for basic research and nanodevices. At metal/insulator interfaces, a configuration commonly found in electronic devices, heat transport strongly depends upon the effective energy transfer from thermalized electrons in the metal to the phonons in the insulator. However, the mechanism of interfacial electron-phonon coupling and thermal transport at metal/insulator interfaces is not well understood. Here, the observation of a substantial enhancement of the interfacial thermal resistance and the important role of surface charges at the metal/ferroelectric interface in an Al/BiFeO3 membrane are reported. By applying uniaxial strain, the interfacial thermal resistance can be varied substantially (up to an order of magnitude), which is attributed to the renormalized interfacial electron-phonon coupling caused by the charge redistribution at the interface due to the polarization rotation. These results imply that surface charges at a metal/insulator interface can substantially enhance the interfacial electron-phonon-mediated thermal coupling, providing a new route to optimize the thermal transport performance in next-generation nanodevices, power electronics, and thermal logic devices.

Preparation of pH-sensitive carboxymethyl cellulose/chitosan/alginate hydrogel beads with reticulated shell structure to deliver Bacillus subtilis natto.

pH-sensitive hydrogels have been applied in delivering probiotics and drugs. However, pH sensitivity has been found to be contradictory with structural stability in hydrogel preparation. In this work, a novel strategy based on two systems of sodium carboxymethyl cellulose (CMC)/chitosan (CS) and sodium alginate (SA)/calcium chloride was designed to construct a reticulated shell structure stable for 3 h in simulated gastric fluid (pH 1.2) but began to break up at 2 h in simulated intestinal fluid (pH 6.8), exhibiting obvious pH sensitivity. The embedding rate of Bacillus subtilis natto reached to 67.3%, and the sustained release lasted for more than 10 h. It is implicated that the reticulated shell structure has harmoniously balanced the two incompatible properties of pH sensitivity and sustained release of CMC/CS/SA beads.

Harnessing digital imaging to detect the transmittance coupled with the uniformity of transparent optical materials.

A digital image (DI) method is reported to determine the transmittance and the uniformity of transparent optical materials (TOMs) at the same time, in which an objective image (OI) with a two dimensional (2D) entropy of 3.45 is scanned using a scanner with a black background. The OI pictures covered without and with a TOM went through gamma correction and color correction. The two corrected pictures were transformed into two matrixes, between which the transparency ratio and the correlation coefficient refer to the transmittance and the uniformity of TOMs. As a result, a p-value of 0.97 and an r value of 0.92 were achieved from the paired T-test between the DI method and the ultraviolet spectrometry (UVS) method, indicating a similar accuracy in determining the transmittance of TOMs between them. In addition, the DI method is a simple and rapid method to evaluate the uniformity of TOMs and to reveal the correlation among transmittance, uniformity and thickness of TOMs, particularly applicable for inhomogeneous TOMs.

A rapid and rapid method to quantify poly (γ-glutamic acid) content via copper ion complexation.

Presently, there have been some limitations in most of methods to determine poly (γ-glutamic acid) (γ-PGA) content because of many impurities in test specimens. It is necessary to establish a rapid and accurate method to quantify γ-PGA content. In this work, γ-PGA and some impurities commonly seen in fermented broth like glucose, glutamic acid and proteins were used to complex with copper ions. The results show that only γ-PGA can make copper ion precipitated, which content linearly correlates with the precipitate amount. From the study on the validity of the method, it is found that the accuracy and precision are 95.82% and 99.29%, much higher than the ones of method UV and weighing. Therefore, the method via the complexation of copper ion will be popularized to determine γ-PGA content in crude biological samples.

Inhibition of nattokinase against the production of poly (γ-glutamic Acid) in Bacillus subtilis natto.

OBJECTIVE: To study the effect of nattokinse (NK) on the synthesis of poly(γ-glutamic acid) (γ-PGA) in Bacillus subtilis natto. RESULTS: γ-PGA yield significantly decreased as NK was added in the original medium. With the increment of NK dosage, the yield decreased increasingly, but biomass increased instead of decreasing. The fact that cell density triggers the synthesis of γ-PGA is a controversial issue. γ-PGA yield and biomass closely correlate with addition time of NK. The later the addition of NK, the more γ-PGA yield decreased but the more biomass increased. It is concluded that cell hunger is a key factor to trigger the transmission of the cell density signal, and NK may inhibit γ-PGA synthesis by alleviating cell hunger. Besides, NK may reduce γ-PGA yield by degrading extracellular γ-PGA molecules. The study of adding L-glutamate of 0-20 g/L to the original medium showed that low concentration of L-glutamate (less than 5 g/L) could promote the synthesis of NK and γ-PGA, and thus NK may inhibit γ-PGA synthesis through strengthening substrate competition. CONCLUSIONS: NK mainly inhibits γ-PGA synthesis in Bacillus subtilis natto through alleviating cell starvation and strengthening substrate competition, and reduces γ-PGA yield through degrading extracellular γ-PGA molecules.

Regulating the Interfacial Electronic Coupling of Fe2 N via Orbital Steering for Hydrogen Evolution Catalysis.

The capability of manipulating the interfacial electronic coupling is the key to achieving on-demand functionalities of catalysts. Herein, it is demonstrated that the electronic coupling of Fe2 N can be effectively regulated for hydrogen evolution reaction (HER) catalysis by vacancy-mediated orbital steering. Ex situ refined structural analysis reveals that the electronic and coordination states of Fe2 N can be well manipulated by nitrogen vacancies, which impressively exhibit strong correlation with the catalytic activities. Theoretical studies further indicate that the nitrogen vacancy can uniquely steer the orbital orientation of the active sites to tailor the electronic coupling and thus benefit the surface adsorption capability. This work sheds light on the understanding of the catalytic mechanism in real systems and could contribute to revolutionizing the current catalyst design for HER and beyond.

Fabrication of a porous chitosan/poly-(γ-glutamic acid) hydrogel with a high absorption capacity by electrostatic contacts.

A porous chitosan (CS)/poly-(γ-glutamic acid) (γ-PGA) hydrogel was prepared by polymerization by electrostatic contacts of CS with γ-PGA without linker. The porosity of the hydrogel remarkably depends on γ-PGA content, pH regulator, and drying way. The optimization of them had given the hydrogel a high swelling capacity of 1398%, 11-fold higher than that of neat CS hydrogel. The hydrogel was applied to recover bovine serum albumin (BSA) from aqueous solution, and its adsorption capacity was influenced by the initial concentration and pH of BSA solution. Based on the studies of kinetics and isotherm, a high equilibrium adsorption capacity (qe = 948 mg/g) and a correlation coefficient of 0.996 were calculated from pseudo-second order kinetic equation, and a high affinitive constant (kF = 472 mL/mg) and a high saturated absorption capacity (qm = 1818.5 mg/g) were observed from Freundlich isotherm equation, indicating the porous hydrogel will be a good absorbent for protein recovery from sewage.

N-induced lattice contraction generally boosts the hydrogen evolution catalysis of P-rich metal phosphides.

P-rich transition metal phosphides (TMPs) with abundant P sites have been predicted to be more favorable for hydrogen evolution reaction (HER) catalysis. However, the actual activities of P-rich TMPs do not behave as expected, and the underlying essence especially at the atomic level is also ambiguous. Our structural analysis reveals the inferior activity could stem from the reduced overlap of atomic wave functions between metal and P with the increase in P contents, which consequently results in too strong P-H interaction. To this end, we used N-induced lattice contraction to generally boost the HER catalysis of P-rich TMPs including CoP2, FeP2, NiP2, and MoP2. Refined structural characterization and theoretical analysis indicate the N-P strong interaction could increase the atomic wave function overlap and eventually modulate the H adsorption strength. The concept of lattice engineering offers a new vision for tuning the catalytic activities of P-rich TMPs and beyond.